Methods of killing nematodes with 6, 9-dioxa-1-spiro[4, 4]nonenes



3,369,966 Patented Feb. 20, 1968 ABSTRACT OF THE DISCLOSURE Thisapplication relates to the use of compounds corresponding to thefollowing formulas as insecticides and nematocides ifili FORMULA AFORMULA B In the above formulas, X represents chlorine or bromine and RR and R are each selected from the class consisting of hydrogen andalkyl, cycloalkyl, phenyl, alkoxyalkyl, phenyloxyalkyl and hydroalkylradicals usually having up to 20 carbon atoms and preferably 1 to carbonatoms. R; is either the structure:

or the structure:

where R R and R are as above.

In the foregoing Formula B, it is to be noted that the substituentsdesignated as R R and R occur more than once in each formula, In theseinstances, each R group may refer to a different radical selected fromthe group set forth, and each R and each R may similarly be different.Such compounds are obtained, for example, when produced by a method inwhich successive reactions with an alcohol are employed and a differentalcohol is used in each step. Compounds of this type are included withinthe scope of the various embodiments of the invention disclosed andclaimed herein.

State of the prior art This application is a continuation-in-part of US.application Ser. No. 234,846, filed Nov. 1, 1962, now abandoned.

The reaction of hexachlorocyclopentadiene with an excess of ethyleneglycol has been reported heretofore by Newcomer and McBee in the Journalof the American Chemical Society, vol. 71', p. 946 (1949). According tothis article, the reaction when carried out at 50 C. to 60 C. producesl,2,3,4,ll,12,13,l4-octachloro-6,9,l5,l8- tetraoxadispiro [4.4.4.4]-l,3,1 1,13-octadecatetraene, which has the formula:

Description 0]" the invention It has now been found that the reaction ofhexahalocyclopentadiene with ethylene glycol or a polyol of the ethyleneglycol type, i.e., having hydroXyl groups on adjacent carbon atoms, canbe carried out in such a way as to produce several products quitedifferent from that reported in the above article which are useful aspesticides. The temperature of the reaction and the amount of basecatalyst employed determines the particular nature of the productobtained.

While the compounds referred to are basically all produced fromhexahalocyclopentadiene and a polyol having adjacent hydroxyl groups inthe presence of a base, they correspond to the general formulas whichare set forth below:

FORMULA B In the above formulas, X represents chlorine or bromine and RR and R are each selected from the class consisting of hydrogen andalkyl, cycloalkyl, phenyl, alkoxyalkyl, phenyloxyalkyl and hydroxyalkylradicals usually having up to 20 carbon atoms, and preferably 1 to 10carbon atoms. R, is either the structure:

or the structure:

the scope of the various embodiments of the invention disclosed andclaimed herein.

In producing the compounds of the formulas set forth above: any polyolhaving hydroxyl groups attached to adjacent carbon atoms can beemployed. Such polyols correspond to the formula:

where R R and R are as defined above; these radicals in the polyolcorrespond to those in the above formulas. Examples of such polyols usedto produce the various compounds above include aliphatic poly'ols suchas ethylene glycol, 1,2-propanediol, 1,2-butanediol, 2-methyl-2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,2-hexanediol,5,.6-decanediol, 2-methyl-3,4-pentanediol and2,2-dimethyl-3,4-butanediol; alicyclic polyols such ascyclohexyl-l,2-ethanediol; aryl-substituted p'olyols such asphenyll,2-ethanediol; alkoXy-substit-uted polyols such asl-methoxy-2,3-propanediol; aryloxy-substituted polyols such asl-phenoxy-2,3-propanediol; and polyols containing additional hydroxylgroups in addition to those on the adjacent carbon atoms, such as1,2,6-hexanetriol. In each instance, the polyol must have at least 2carbon atoms, and for most purposes it is preferred to use polyolshaving a total of between 2 and 30 carbon atoms in which each R group iseither hydrogen or alkyl of up to 20 carbon atoms. It has been foundfurther that the reaction is best carried out with polyols in which thehydroxyl groups are both bonded to either primary or secondary carbonatoms, i.e., polyols in which R; is hydrogen.

The alcohols employed in preparing the compounds of this invention maycontain additional substituents which do not prevent the reaction. Ascan be seen from the above, even compounds having more than two bydroxylgroups may be employed. The preferred alcohols comprise compoundscontaining only carbon, hydrogen and oxygen.

Hexahalocyclopentadiene, as used throughout the specification, refers toa chloroor bromo-substituted cyclopentadiene, for example,hexachloropentadiene or hexabrom'ocyclopentadiene.

The reactions to produce the compounds of this invention arebase-catalyzed. While essentially any base catalyst, as that term isunderstood in the art, can be used, it is preferred to employ inorganicbases, including the hydroxides, alkoxides and oxides of metals such aslithium, ptassium, sodium, calcium, magnesium and the like. The metalsthemselves, e.g., metallic sodium, can also be employed, and providequite satisfactory results. Organic bases such as amines are lesssatisfactory since they tend to reduce the yield by promoting sidereactions which compete with the desired reaction. The most desirablebases from an economic standpoint are the hydroxides of the alkalimetals and these also provide the best results.

As is more fully set forth hereinbelow, the amount of base employed, aswell as the temperature at which the reaction is carried out, determinesthe particular nature of the product resulting from the reaction of thehexahalocyclopentadiene and the polyol. Aside from these, however, otherreaction conditions are not critical and may be varied widely. Forexample, the reaction can be carried out in the presence of a solvent ifdesired, although quite often the excess polyol orhexahalocyclopentadiene is used as the only solvent. Other inertsolvents such as ethylene glycol dimethylether, diethylene glycoldimethylether, tetrahydrofuran, acetamide, and the like, can be usedwith similar effectiveness, and when the polyol employed is a solid, itis often desirable to have a solvent present.

The compounds corresponding to Formula A above are produced by thereaction of hexahalocyclopentadiene with a polyol in the presence of abase, as defined above. The temperature at which the reaction is carriedout is below about 50 C. and preferably below about 35 C. in order toobtain the product in good yield. The temperature may also be below roomtemperature, for instance, 0 C. or lower, if desired.

Compounds of Formula B above are also produced during the reaction asdescribed above the produce compounds of Formula A, although the yieldis usually very low unless sufiicient polyol, i.e., at least about 2moles per mole of hexahalocyclopentadiene, as well as sufiicient base,again at least about 2 moles per mole of hexahalocyclopentadiene, areemployed.

Using these proportions of reactants, good yields of compounds of theFormula B are produced and, while low temperatures such as thosedescribed above can be used, the reaction may also be carried out attemperatures up to about C. or higher, and it is preferred to usetemperatures of at least about 50 C. The Formula B compounds are alsoconveniently made by reaction of compounds of the Formula A withadditional polyol in the presence of additional base, using temperaturesbe tween about 40 C. and about 120 C. This reaction can be carried outwith a different alcohol from that used to make the compound of theFormula A; it may be any alcohol, either monohydric or polyhydric, andhaving the hydroxyl groups either 'on adjacent or non-adjacent carbonatoms. For example, in addition to those polyols enumerated above,polyols such as 1,3-propanediol, 1,4- butanediol,2,2-dimethyl-1,3-propanediol, trimethylolpropane, pentaerythritol,polyethylene glycols and the like, as well as monohydric alcohols suchas methanol, ethanol, heptanol and octanol, and other alcohols of theformula:

Ri-C OH 1'1 where R, and R are as above, can be employed. When CompoundA is reacted further with a polyol having hydroxyls on adjacent carbonatoms, the R group in Formula B has the structure:

where R R and R are again derived from the polyol and are as definedabove. When, however, a monohydric alcohol or a polyol having hydroxylson non-adjacent atoms is used in making the compound of the Formula B,the R group 'of the structure:

where R and R are as defined above. In these instances, one hydroxylgroup from each of two alcohol molecules reacts with thehexahalocyclopentadiene nucleus, whereas in the case of the polyolhaving adjacent hydroxyl groups, both hydroxyl groups reacting with thehexahalocycloentadiene are attached to the same polyol molecule.

The compounds of Formula B can also be produced by changing the order ofreaction, that is, by first reacting hexahalocyclopentadiene with themonohydric alcohol to produce a compound of the structure:

and then reacting this compound with the polyol.

It may be noted that the double bond in Formula B is shown in the3-position. However, depending upon the particular reactants andreaction conditions, the double bond in all or part of the productobtained in particular cases maybe in the 2-position. The compounds areconsidered equivalent for purposes of this invention, and names andformulas herein are intended to include both isomers as well as themixture.

It may be noted that the ranges of conditions and proportions whichproduce the several compounds depicted above overlap. In such instances,mixtures of the different products may be obtained; however, by properchoice of the conditions and proportions, good yields of any of theabove compounds are achieved.

The several compounds to which this invention relates will be furtherdescribed by reference to the following examples. These examples, beingillustrative, should not be construed as limiting the invention to theirdetails.

Example I.] ,2,3,4-tetrachl0r06,9-di0xa-1,3-

spir0[4.4] nonadiene A two-liter, round bottom flask was charged withone mole of hexachlorocyclopentadiene. A solution of 137 grams (2.10moles, 85 percent purity) of potassium hydroxide in ethylene glycol(496.0 grams, 8.0 moles) was added dropwise at 25 C. to 33C. Whentwo-thirds of the glycol solution had been added, there was one liquidphase and some precipitated potassium chloride. The r mainder of thesolution was added and the reaction mixture was stirred at 25 C. to 30C. for 20 hours; the pH was then 8.0. One liter of water was added andthe layers were separated. The water layer was extracted with ether andthe combined organic layers were washed with saturated sodium chloridesolution and the organic solvent removed under vacuum. When the organiclayer was nearly evaporated to dryness, ligroin was added and thesolution cooled to 78 C. and filtered. There was obtained 206 grams ofthe above product.

Analysis.--Calculated for C H Cl O Calculated, percent Found, percentCarbon 32.01 31.97 Hydrogen 1.54 1.63 Chlorine 54.15 54.02

Obviously, when hexabromocyclopentadiene is employed, the tetrabromoequivalent will be formed.

Example II.-1,2,3,4-tetrachl0ro-7-methyl-6,9- dioxa-1 ,3 -spir0 [4 .4 1nonadi ene A three-necked, two-liter, round bottom flask was chargedwith one mole (73 grams) of hexachlorocyclopentadiene, 2 moles (152.0grams) of 1,2-propanediol and 300 milliliters of dimethoxyethane. Tothis solution 2.0 moles (132.4 grams, 85 percent purity) of potassiumhydroxide were added in portions while the temperature was kept at 26 C.to 33 C. by external cooling. It took 45 minutes for the addition. Theheterogeneous mixture was stirred at 26 C. overnight; the resultantsolution had a pH of 8.5. To this solution, water was added and theorganic layer was washed with water six times, dissolved in ether andfiltered through Celite. After the solvent was removed at roomtemperature in vacuo, there was obtained 25 grams of crude product whichwas distilled to give pure1,2,3,4-tetrach1oro-7-methyl-6,9-dioxa-1,3-spiro [4.4]nonadiene, boilingpoint 80C. at 0.07 millimeter,

as identified by gas chromatographic analysis. Upon carefuldistillation, the pure sample boiled at 69C. at 0.04 milliliter.

Analysis.Calculated for C H Cl O Calculated, percent Found, percentCarbon 34.82 34.82 Hydrogen 2.19 2.32 Chlorine 51.40 51.38

The use of hexabromocyclopentadiene will produce 1,2,3,4 tetrabrorno 7methyl-6,9-dioxa-1,3-spiro[4.4] nonadiene.

Example III.I,2,3,4-tetrachlor07,8-dimethyl-6,9-dioxa- 1,3-spir0[4.4]-n0nadz'ene To a three-necked, two-liter, round bottom flask containing135 grams (1.5 moles) of 2,3-butanediol, 273 grams (1 mole) ofhexachlorocyclopentadiene and 300 milliliters of dimethoxyethane, solidpotassium hydroxide (132.4 grams, 2 moles, percent purity) was added inportions with external cooling, while the temperature was kept at 30 C.The addition took 45 minutes and the reaction mixture was stirredovernight at 26 C. Water was then added, whereupon an oily productprecipitated which was separated and washed with water. Ether was addedand the soltuion was washed with saturated sodium chloride solutionuntil neutral. After evaporation of the solvent under vacuum at roomtemperature, there remained a crude product, 10 grams of which wasdistilled to give 6.65 grams of a fraction boiling at 60 C. to 100 C. at0.1 millimeter, which was recrystallized from petroleum ether (boilingpoint 35 C. to 60 C.) at solid carbon dioxide temperature five times togive the pure product which melted at 40 C. to 405 C.

Analysis.Calculated for C H Cl O Calculated, Found,

The use of hexabromocyclopentadiene will produce 1,2,3, 4 tetrabromo 7,8dimethyl 6,9 dioxa 1,3 spiro [4.4]nonadiene.

To produce the compounds of this invention, the polyol must have atleast two hydroxyl groups on adjacent carbon atoms. If the only hydroxylgroups in the polyol are on non-adjacent carbon atoms, products of acompletely different class are obtained, as is disclosed in copendingapplication Ser. No. 234,847, filed Nov. 1, 1962. However, the polyolused herein may have hydroxyls on non-adjacent carbon atoms in additionto those hydroxyls on adjacent carbon atoms, and the products obtainedare as described herein, although the yields may be reduced by thecompeting reaction taking place with the adjacent hydroxyl groups. Setforth below is an example of the reaction using such a polyol.

Example I V.-7 4 '-hydr0xybutyl ,2,3,4-tetrachl0r0-6, 9-di0xaspiro [4.4]nona-l ,3-d1'ene To a two-liter, three-necked flask were added 675 grams(5 moles) of 1,2,6-hexanetriol and 64.4 grams (0.97 mole, 85 percentpurity) of solid potassium hydroxide in portions at C. to C. Thesolution was cooled and hexachlorocyclopentadiene (137.0 grams, 0.50mole) was added dropwise at 23 C. to 28 C. while the flask was cooledexternally. After the addition, the reaction mixture was stirred at 30C. for 24 hours (pH was then 8.0). The product was extracted with 500milliliters of ligroin (boiling point 60 C. to 78 C.) to remove 19.2grams of the unreacted hexachlorocyclopentadiene. Chloroform was addedand the mixture was then washed with saturated sodium chloride solutionuntil neutral. The solvent was removed in vacuum to give 148 grams of amixture of 7(4 hydroxybutyl) 1,2,3,4 tetrachloro 6,9dioxaspiro[4.4]-nona-1,3-diene, the desired product, and 5,5- bis( 5,6dihydroxyhexyloxy) 1,2,3,4 tetrachloro 1,3- cyclopentadiene. Theproducts were analyzed by ultraviolet light absorption and infraredexamination.

In a similar manner, the following compounds are likewise formed:

1,2,3 ,4-tetrachloro-7,7,8-trimethyl-6,9-dioxa-1,3-spiro [4.4] nonadiene1,2,3,4-tetrabromo-7,7,8-trimethyl-6,9-dioxa-1,3-spiro [4.4] nonadiene1,2,3 ,4-tetrachloro-7-cyclohexy1-6,9-dioxa-1,3 -spiro [4.4]

nonadiene 1,2,3 ,4-tetrabromo-7-cyclohexyl-6,9-dioxa-1,3-spiro [4.4]

nonadiene 1,2, 3,4-tetrachloro-7-phenyl-6,9-dioxa-1,3-spiro [4.4]

nonadiene 1,2, 3,4-tetrabromo-7-phenyl-6,9-dioxa- 1, 3-spiro 4.4]

nonadiene 1,2,3 ,4-tetrachloro-7-methoxy-8-methyl-6,9-dioxa-1,3-

spiro [4.4] nonadiene 1,2,3,4-tetrabromo-7-methoxy-8-methyl-6,9-dioxa-1,3-

spiro [4.4] nonadiene 1,2,3 ,4-tetrachloro-7-phenoxy-8-methyl-6,9-dioxa-1 ,3-

spiro [4.4] nonadiene 1,2, 3 ,4-tetrabromo-7-phenoxy-8-methyl-6,9-dioxa-1 ,3-

spiro [4.4] nonadiene The above examples illustrate the compounds of theinvention corresponding to Formula A. Below are several examples ofproducts corresponding to Formula B. Examples V to VII demonstrate thesecompounds of Formula B which are produced from polyols, whereas Examples8 and 9 demonstrate the similar compounds made from monohydric alcohols.

Example V.1,2,4-trichlr0-3-ethylen'edi0xy-6,9-di0-xa- 1-spiro[4.4]noneneAn ether solution of 1,2,3,4-tetrachloro- 6,9-dioxa-1,3spiro[4.4]nonadiene (0.20 mole, 52.4 grams) was added slowly at 65 C. toa flask containing 74.4 grams (1.20 moles) of ethylene glycol and 31.2grams (0.60 mole, 85 percent purity) of potassium hydroxide. The etherwas removed continuously during the addition by distillation at 20millimeters vacuum. After all of the nonadiene was added and most of theether was removed, the mixture was stirred at 65 C. to 70 C. for 22.5hours. The reaction product was cooled slowly to room temperature, waterwas added, and the heterogeneous mixture was filtered. A solid wascollected by filtration and was then distilled to give 34.4 grams ofpure product, boiling point 120 C. to 130 C. at 0.04 millimeter. It wasidentified by gas chromatographic and infrared analysis, as well aschemical analysis.

Analysis.Calculated for C H Cl O The use of1,2,3,4-tetrabrom0-6,9-dioxa-1,3 -spiro[4.4]- nonadiene produces1,2,4-tribromo-3-ethylenedioxy-6,9- dioxal-spiro [4.4] nonene.

Example Vl.l ,2,4-trichloro-3- 1,2-pr0pylenedioxy) 7 -methyl-6,9-!dioxa-1 -spz'r0 [4 .4 nonene A three-necked, five-liter flask wascharged with 12.1 moles (920 grams) of propylene glycol. Potassiumhydroxide (10.7 moles, 600 grams, 85 percent purity) was added inportions until all was dissolved. To this solution 575 milliliters ofdimethoxyethane and 250 milliliters of ligroin were added, and themixture was refluxed at 62 C. Hexachlorocyclopentadiene (2 moles, 545.6grams) was added dropwise to the refluxing mixture; the temperature wentto 64 C. After all of the hexachlorocyclopentadiene was added, themixture was stirred and re fluxed at 59 C. for several hours whileremoving 35 milliliters of water. The product was then mixed with oneliter of water and neutralized with dilute hydrochloric Cir acid. Theorganic layer was washed with water and dried on a stream bath invacuum. The oily residue was distilled and 342.6 grams of the productwas collected at 0.1 to 0.45 millimeter. This crude product wasredistilled to give 224.4 grams of the pure product, boiling point 102C. at 0.038 millimeter pressure.

Analysis.Calculated for C H CI O Calculated, percent Found, percentCarbon 41.86 41.86 Hydrogen 41.15 4.15 Chlorine 33.70 33.71

The use of hexabromocyclopentadiene produces1,2,4-tribromo-3-(1,2-propylenedioxy)-7-methyl 6,9 dioxa 1- spiro [4.4]nonene. 1

Example VII The same compound as in Example VI was also prepared byfurther reaction of 1,2,3,4-tetrachloro-7-methyl-6,9-dioxa-1,3-spiro[4.4]nonadiene with propylene glycol in the presenceof potassium hydroxide, as follows: Four grams of potassium hydroxidewere disssolved in 100 milliliters of propylene glycol at C. To thissolution was added a solution of 4.95 grams of 1,2,3,4-tetrachloro-7-methyl-6,9-dioxa-1,3-spiro[4.4]nonadiene in 5.0 milliliters ofdiamethoxyethane and the mixture was stirred for 20 hours at 60 C. Waterand ether were then added to the reaction product and the ether layerwas washed with water until neutral. The ether layer was then dried overanhydrous sodium sulfate and evaporated to yield 4.20 grams of an oilyresidue, which boiled at 120 C. at 0.1 millimeter and which wasidentified by infrared analysis as1,2,4-trichloro-3-(1,2-propylenedioxy)-7-methyl-6,9-dioxa-1-spiro[4.4]nonene.

The use of 1,2,3,4-tetrabromo-7-methyl-6,9-dioxa-1,3-spiro[4.4]nonadiene produces 1,2,4-tribromo-3-(1,2-propylenedioxy)-7-methy1-6,9-dioxa 1 -spiro [4.4] nonene.

Example VIII.3,3-dim;eth'0xy-1,2,4-trichl01'0-6,9- dioxa-I -spir0 [4 .4nonene A three-necked, 500-milliliter, round bottom flask was chargedwith 54.4 grams (1.7 moles) of methanol and 31.2 grams (0.6 mole,percent purity) of potassium hydroxide. At 65 C. to 70 C.,1,2,3,4-tetrachloro-6,9- dioxa-1,3-spiro[4.4]nonadiene (52.4 grams, 0.20mole) in 60 milliliters of dimethoxyethane was added dropwise. Thereaction mixture was stirred at 65 C. for 2 hours. Water and ether wereadded to the cooled product and the organic layer was washed with waterthree times, dried and distilled, yielding 54.5 grams of a fractionboiling at 88 C. to 90 C. at 0.03 to 0.035 millimeter. The distillatewas added to petroleum ether (boiling point 35 C. to 60 C.) and thecrystallized product was filtered. The solid, melting point 51 C. to 63C., was crystallized three times from ligroin to give 29.5 grams of theproduct, which melted at 675 C. to 68.5 C.

A.n1alysis.Calculated for C H Cl O Calculated, percent Found, percentCarbon 37.33 37.73 Hydrogen 3.83 3.85 Chlorine 36.74 36.89

The use of 1,2,3,4-tetrabrorno-6,9-di0xa-l,3 -spiro[4.4]- nonadieneproduces 3,3-dimethoxy-1,2,4-tribromo-6,9-dioxa-1-spiro[4.4]nonene.

Example IX The same compound produced in Example VIII was made asfollows: Hexachlorocyclopentadiene was reacted with methanol in thepresence of potassium hydroxide to produce1,2,3,4-tetrachloro-5,5-dimethoxycyclopentadiene (52.8 grams, 0.20mole), which was then added at C. to a flask containing 74.4 grams (1.20moles) of ethylene glycol and 31.2 grams (0.60 mole, 85 percent purity)of potassium hydroxide. The mixture was stirred for 2 hours andfiltered. 12.5 grams of potassium chloride was separated. The filtratewas mixed with water and ether, and the ether layer was separated andwashed until neutral. Crystallization from ligroin gave 48.5 grams ofproduct, melting point 67 C. to 68.5 C. The 3,3 dimethoxy 1,2,4trichloro-6,9-dioxa-1-spiro[4,4] nonene was identified by mixed meltingpoint, infrared spectra and gas chromatography.

The use of hexabromocyclopentadiene produces 3,3- dimethoxy 1,2,4,tribromo 6,9 dioxa 1 spiro[4.4]

nonene.

In the manner of the above two-stage examples, the following compoundscan also be prepared by further reacting 1,2,3,4tetrachloro-6,9-dioxa-1,3-spiro[4,4]nonadiene or 1,2,3,4 tetrabromo6,9-dioxa-1,3-spiro[4.4] nonadiene with the appropriate alcohol:

1,2,4-trichloro-3 1,2-hexanedioxy) -6,9-dioxa-1-spiro [4.4] nonene1,2,4-tribromo-3 (1,2-hexanedioxy)-6,9-dioxa-1-spiro [4.4] nonene1,2,4-trichloro-3 (cyclohexyl-1,Z-ethanedioxy) -6,9-

dioxa-1-spiro[4.4]nonene 1,2,4-tribromo-3 (cyclohexyl-1,2-ethanedioxy)-6,9-

dioxa-1-spiro[4.4]nonene 1,2,4-trichloro-3 (phenyl-1,2-ethanedioxy)-6,9-dioxa- 1-spiro[4.4] nonene 1,2,4-tribromo-3(phenyl-1,2-ethanedioxy) -6,9-dioxa- 1-spiro[4.4]nonene1,2,4-trichloro-3 (methoxy-2,3-propanedioxy -6,9-

dioxa-1-spiro[4.4]nonene 1,2,4-tribromo-3 (methoxy-2,3 -prop anedioxy)-6,9-

dioxa-1-spiro[4.4]nonene 1,2,4-trichloro-3 phenoxy-2,3-propanedioxy -6,9

dioxa-1-spiro[4.4] nonene 1,2,4-tribromo-3 (phenoxy-2,3-propanedioxy)-6,9-

dioxa-1-spiro[4.4]nonene 1,2,4-trichloro-3 (6-hydroxy-1,2-hexanedioxy)-6,9-

dioxa-1-spiro[4.4] nonene 1,2,4-tribromo-3 (6-hydroxy-1,2-hexanedioxy)-6,9-

dioxa-1-spiro[4.4] nonene 1,2,4-trichloro-3,3 -bis(4-hydroxy-1-butoxy)-6,9-

dioxa-1-spiro[4.4] nonene 1,2,4-tribromo-3 ,3-bis (4-hydroxyl-butoxy)-6,9-

dioxa-1-spiro[4.4]nonene 1,2,4-trichloro-3, 3 (dioctyloxy)-6,9-dioxa-1-spiro [4.41nonene 1,2,4-tribromo-3,3 (dio ctyloxy-6,9-dioxa-1-spiro [4.4] nonene While the examples show specificreactants, all the polyols and alcohols enumerated in the specification,as well as not specifically enumerated, are reactive in a similar mannerto produce compounds within the scope of the invention.

Likewise, while the above examples demonstrate the invention usinghexachlorocyclopentadiene, other hexahalocyclopentadienes, such ashexabromocyclopentadiene, and including cyclopentadiene derivativescontaining different halogens in the same molecule, such as 1,2-dibromo3,4,5,5 tetrac'hlorocyclopentadiene and2,3-dibromo-1,4,5,5-tetrachlorocyclopentadiene are also contemplated foruse herein and produce corresponding halogen-containing products.Similarly, although for clarity the invention has been described andexemplified using a single alcohol in each reaction step, mixtures ofpolyols or, in the appropriate instances, mixtures of monohydroxyalcohols can be employed.

The compounds of this invention are useful in several variedapplications. They find utility, for example, as insecticides andnematocides. To exemplify their activity in this regard, the compound ofExample VIII, applied as a 2.5 percent solution in acetone topically tothe thorax of housefiies (Wilson), effectively killed the flies. Thenematocidal activity of the compounds described herein was shown bytests such as one in which the compounds of Example I was applied as asolution in an acetonewater mixture to a suspension of Panagrellusnematodes in water (500 to 750 nematodes per milliliter). It was foundthat this treatment was extremely effective in destroying the nematodes,even using very low concentrations of the compound, e.g. .0001 percent.

While specific examples are given, all the compounds of the genusdescribed in the specifications and claims will show efficacy asinsecticides or nematocides.

In addition to their use as insecticides and in related applications,the compounds of the invention have various other uses, depending upontheir particular properties. For example, compounds of formula A andFormula B react with olefinic compounds to produce Diels-Alder additionproducts that can be utilized in making resinous materials in whichhalogens are sought to be introduced. For example, the reaction of thecompound of Example II with maleic anhydride results in a material fromwhich polyester resins can be obtained.

According to the provisions of the patent statutes, there are describedabove the invention and what are now considered to be its bestembodiments. However, within the scope of the appended claims, it is tobe understood that the invention may be practiced otherwise than asspecifically described.

I claim:

1. A method of killing nematodes which comprises subjecting them to alethally effective concentration of a nematocidal composition comprisingas an essential ingredient a compound of the formula:

where X is halogen and R R and R are each selected from the classconsisting of hydrogen and alkyl, cycloalkyl, phenyl, alkoxyalkyl,phenyloxyalkyl and hydroxyalkyl radicals.

2. A method of killing nematodes as in claim 1 which comprisessubjecting them to a lethally eifective concentration of nematocidalcomposition comprising as an essential ingredient the compound 1,2,3,4-tetrachloro-6,9' dioxa-1,3-spiro[4.4]nonadiene.

References Cited UNITED STATES PATENTS 2,799,616 7/1957 Johnson 16733ALBERT T. MEYERS, Primary Examiner.

S. FRIEDMAN, Assistant Examiner.

